WO2001011113A1 - Black ruthenium plating solution - Google Patents

Black ruthenium plating solution Download PDF

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Publication number
WO2001011113A1
WO2001011113A1 PCT/JP2000/003395 JP0003395W WO0111113A1 WO 2001011113 A1 WO2001011113 A1 WO 2001011113A1 JP 0003395 W JP0003395 W JP 0003395W WO 0111113 A1 WO0111113 A1 WO 0111113A1
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black
ruthenium
plating
plating solution
solution
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PCT/JP2000/003395
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French (fr)
Japanese (ja)
Inventor
Akihiro Aiba
Tomoharu Mimura
Toshikazu Okubo
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Nikko Materials Company, Limited
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Publication of WO2001011113A1 publication Critical patent/WO2001011113A1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/50Electroplating: Baths therefor from solutions of platinum group metals

Definitions

  • the present invention relates to a black ruthenium plating solution capable of maintaining a strong blackness with a high ruthenium adhesion by stabilizing a thioic compound as a color former at the anode during electrolysis.
  • a platinum-plated titanium plate is used as an anode
  • an object to be coated is used as a cathode, and these are immersed in the above-mentioned plating solution and energized to deposit a plating film on the cathode.
  • the ruthenium plating film can be colored black by the action of a coloring agent contained in the solution, and as the coloring agent, a thioic compound is particularly excellent.
  • the black coating is particularly valuable as a decorative coating for watches, eyeglass frames, dials, lighter cases, lipstick caps, etc. or as an industrial material such as electrical contacts, reflectors, and heat absorbers.
  • JP-B-63-99027 and JP-A-63-259,095 are known.
  • the conventional black ruthenium plating solution is characterized in that the solution is easy to manage, has a high luster, has good adhesion to the substrate, and is excellent in corrosion resistance and abrasion resistance.
  • the characteristics of the conventional black ruthenium plating solution that is, the features that the solution is easy to manage, and that it is glossy, has good adhesion to the substrate, and is excellent in corrosion resistance and abrasion resistance. It is an object of the present invention to suppress the decomposition of the thio compound to be added as a color former due to anodic oxidation during electrolysis, to maintain a strong blackness during the electrolysis process, and to obtain a stable black plating. . Disclosure of the invention
  • the present inventor has found that the cause of the decrease in blackness in such black ruthenium plating is that the thio compound which is a color former is oxidized at the anode during electrolysis and loses its effect. It has been found that by stabilizing the thio compound in the solution, the ruthenium plating film is maintained at a high level and blackness.
  • Black ruthenium plating solution containing ruthenium sulfate, sulfamic acid, a thio compound and a sacrificial oxidizing agent added to prevent thio compounds from being anodized during electrolysis as components in the solution.
  • a sacrificial oxidizing agent is added to the ruthenium plating solution in order to prevent the formation of a thioic compound due to the positive electrode during electrolysis.
  • the oxidation reaction of the sacrificial oxidant proceeds as the main reaction at the anode, and the oxidation reaction of the thio compound hardly occurs.
  • the action and effect of the thio compound for blackening the plating film do not deteriorate.
  • the thioic compound had to be added frequently as described above. A strong blackness can be maintained without replenishing the compound.
  • the black ruthenium plating solution of the present invention contains norethenium sulfate, sulfamic acid, a thio compound, and a sacrificial oxidizing agent added to prevent decomposition of the thio compound due to anodic oxidation during electrolysis.
  • Ruthenium sulfate becomes a source of ruthenium metal that precipitates as plating, and the ruthenium concentration is from 1 to 10 g ZL.
  • Current efficiency, plating time and loss of ruthenium due to washing of electrodeposits during handling (so-called “pumping”) ) Is desirable. However, it is not particularly limited to this concentration.
  • Sulfamic acid suppresses the instability of ruthenium ion valence due to anodic oxidation and cathodic reduction when ruthenium sulfate is used, prevents the formation of non-metallized, low-valent ruthenium, and provides stable ruthenium. It enables plating work.
  • An appropriate concentration is 50 to 150 g / L, but it is not particularly necessary to limit the concentration.
  • the thioic compound is added to blacken the color tone of the ruthenium plating 3 ⁇ 4.
  • the thio compound is selected from thiourea, a thiourea derivative, a compound having a mercapto group, thiomalic acid, ammonium thiocyanate, and the like.
  • thiourea is most suitable in view of the stability and price of the compound.
  • concentration of the thio compound the stronger the blackness is obtained, but if the concentration is too high, the solution becomes unstable.
  • a suitable concentration is 0.1 to 10 Og / L, particularly 1.0 to 5.0 g / L.
  • a sacrificial oxidizing agent added to prevent the decomposition of the thio compound due to anodic oxidation during electrolysis, a sacrificial oxidizing agent that is more susceptible to anodic oxidation than the thio compound is used.
  • the compound itself undergoes anodization during electrolysis and changes and is consumed, but it is necessary that the compound itself and the oxidized compound do not affect the ruthenium deposition reaction.
  • the sacrificial oxidizing agent include hydroxylamine sulfate, formalin, and ascorbic acid.
  • hydroxylamine sulphate is the most effective because it remains in the solution even when acidified and does not affect the coating.
  • the sacrificial oxidizing agent has an effect of preventing oxidation of the thio compound if it is substantially present in the solution. Therefore, the concentration of the sacrificial oxidizing agent is not particularly limited, but usually 0.1 to 100 g L. Appropriate.
  • the pH, the current density, and the solution temperature can be appropriately adjusted and used. Specifically, it is appropriate that the pH is less than 2, the current density is 5 to 15 AZdm, and the liquid temperature is 40 ° C or higher.
  • the substrate (material) on which the black ruthenium plating of the present invention is performed is suitably a nickel plating plated with flash plating.
  • platinum or platinum-plated titanium is used as the anode.
  • these conditions should be appropriately selected by the trader according to the equipment and the shape of the covering object, and need not be particularly limited. Examples and comparative examples
  • this solution was divided into 3 parts, and 2 parts each were added with 10 gZL of hydroxylamine sulfate and 50 gZL as a sacrificial oxidizing agent, respectively, to obtain Examples 1 and 2, and the remaining 1 part was not added. This was used as a comparative example.
  • Plating was repeatedly performed using these three solutions.
  • the plating conditions are as follows.
  • the material used was a brass plate plated with Ni in a normal watt bath and flash-flashed.
  • Example 1 since a large amount of sacrificial oxidizing agent, hydroxylamine was added, it was not necessary to supply the same agent during black ruthenium plating, but in Example 2, sacrificed during electrolysis. Since the amount of hydroxylamine sulfate, which is an acidifying agent, was small in the initial stage of plating and was consumed with plating, replenishment was performed to maintain the concentration.
  • hydroxylamine sulfate as the sacrificial oxidizing agent of the present invention, it became possible to stably obtain a plating film having a strong blackness in black ruthenium plating.
  • a sacrificial oxidizing agent such as hydroxynoramine sulfate did not hinder the formation of a black ruthenium plating film.
  • Hydroxylamine sulfate was the most effective as a sacrificial oxidizing agent, but other sacrificial oxidizing agents of the present invention obtained almost the same effect. Similar results were obtained with thio compounds other than thiourea.
  • the reason why the blackness of black ruthenium plating decreases is that the thio compound, which is a color former, is oxidatively decomposed at the anode during electrolysis and loses its effect.By stabilizing the thio compound in the solution, The ruthenium plating film can maintain a strong blackness. Therefore, a sacrificial oxidizing agent is added to the black ruthenium plating solution to prevent decomposition of the thio compound due to anodic oxidation during electrolysis. As a result, at the anode, the oxidation reaction of the sacrificial oxidant proceeds as a main reaction, and the oxidation reaction of the thio compound hardly occurs.
  • the characteristics of the conventional black ruthenium plating solution that is, the easy management of the solution, the glossiness, good adhesion to the substrate, and excellent corrosion resistance and abrasion resistance are the original characteristics of the black ruthenium plating solution.
  • the sacrificial acid suppresses the thiol conjugate added as a coloring agent by anodic oxidation during electrolysis, and maintains a strong blackness during the electrolysis process. It has an excellent effect that a stable black plating can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

A black ruthenium plating solution, characterized as containing, as effective components in the solution, ruthenium sulfate, sulfamic acid, a thio compound and a sacrificial oxidizing agent being added for preventing the decomposition of the thio compound due to anodic oxidation. The plating solution can be used for inhibiting the decomposition of a thio compound being added as a color former due to anodic oxidation, to thereby maintain dense blackness during electrolysis and thus provide a stable black plating, while keeping the desirable characteristics of a conventional black ruthenium plating solution that it can be controlled with ease, has good gloss, exhibits good adhesion to a substrate, and is excellent in the resistance to corrosion and abrasion.

Description

明 細 書 黒色ルテニウムめっき液 技術分野  Description Black ruthenium plating solution Technical field
本発明は、 電解中に陽極において発色剤であるチオイヒ合物を液中で安定化する ことによって、 ルテニウムめつき«が強い黒色度を維持することができる黒色 ルテニウムめっき液に関する。 背景技術  The present invention relates to a black ruthenium plating solution capable of maintaining a strong blackness with a high ruthenium adhesion by stabilizing a thioic compound as a color former at the anode during electrolysis. Background art
ルテニウムめっき液としては、 ルテニウム錯塩を用いるもの、 塩化ルテニゥ ムを用いるもの、 硫酸ルテニウムを用いるものが知られている。  As ruthenium plating solutions, those using ruthenium complex salts, those using ruthenium chloride, and those using ruthenium sulfate are known.
これらは、 主に、 白金めつきチタン板を陽極とし、 被めつき物を陰極として、 これらを上記めつき液に浸漬して通電することにより、 陰極にめっき被膜を析出 させるものである。  In these methods, a platinum-plated titanium plate is used as an anode, an object to be coated is used as a cathode, and these are immersed in the above-mentioned plating solution and energized to deposit a plating film on the cathode.
ルテニウムめっき被膜は、 液中に含有せしめた発色剤の作用により、 黒色に 発色させることができるが、 この発色剤としては特にチオイヒ合物が優れている。 黒色めつき被膜は、 時計側、 めがねフレーム、 文字盤、 ライターケース、 口 紅キャップ等の装飾めつきあるいは電気接点、 反射鏡、 吸熱体等の工業用材とし て特に価値が高い。 この黒色ルテニウムめっき液の有効な技術の例として、 特公 昭 6 3— 9 0 2 7及び特開昭 6 3 - 2 5 9 0 9 5が知られている。  The ruthenium plating film can be colored black by the action of a coloring agent contained in the solution, and as the coloring agent, a thioic compound is particularly excellent. The black coating is particularly valuable as a decorative coating for watches, eyeglass frames, dials, lighter cases, lipstick caps, etc. or as an industrial material such as electrical contacts, reflectors, and heat absorbers. As examples of effective techniques for the black ruthenium plating solution, JP-B-63-99027 and JP-A-63-259,095 are known.
従来の上記黒色ルテニウムめっき液は、 液の管理が容易であり、 しかも光沢 を有し基材との密着性がよく、 耐食性及び耐摩耗性に優れているという特徴があ る。  The conventional black ruthenium plating solution is characterized in that the solution is easy to manage, has a high luster, has good adhesion to the substrate, and is excellent in corrosion resistance and abrasion resistance.
ところが、 大きな問題が 1つあり、 それは添加するチォ化合物の発色剤とし ての特性あるいは機能を維持することが難しく、 電解中の陽極酸化によってチォ 化合物が し、 電解の進行とともに黒色度は薄くなって行く傾向があることで ある。 このようなことから、 黒色ルテニウムめっき液によるめつきの際黒色度が安 定せず、 従来は黒色ルテニウムめっき初期の黒色度を維持しようと思えば、 頻繁 にチォ化合物を添加しなければならなかった。 However, there is one major problem: it is difficult to maintain the properties or functions of the added thio compound as a color former, and the thio compound is destroyed by anodic oxidation during electrolysis, and the blackness decreases with the progress of electrolysis. That is the tendency to go. For this reason, the blackness is not stable when plating with the black ruthenium plating solution, and in the past it was necessary to frequently add a thio compound to maintain the initial blackness of black ruthenium plating. .
これは生産効率を著しく低下させるという問題があり、 実際上このような生 産システムを組むことは難しいために、強レ、黒色度が要求される分野においても、 低下した薄レ、黒色度で妥協せざるを得なレ、場合があつた。  This has the problem of significantly lowering production efficiency, and it is difficult to construct such a production system in practice. I had to compromise, sometimes.
上記のことから、 従来の黒色ルテニウムめっき液の特性、 すなわち液の管理が 容易であり、 しかも光沢を有し基材との密着性がよく、 耐食性及び耐摩耗性に優 れているという特徴を生かすと共に、 発色剤として添加するチォ化合物が電解中 の陽極酸化によって分解するのを抑制し、 電解の工程中において強い黒色度を維 持して、 安定した黒色めつきを得ることを課題とする。 発明の開示  From the above, the characteristics of the conventional black ruthenium plating solution, that is, the features that the solution is easy to manage, and that it is glossy, has good adhesion to the substrate, and is excellent in corrosion resistance and abrasion resistance. It is an object of the present invention to suppress the decomposition of the thio compound to be added as a color former due to anodic oxidation during electrolysis, to maintain a strong blackness during the electrolysis process, and to obtain a stable black plating. . Disclosure of the invention
本発明者は、 このような黒色ルテニウムめっきにおける黒色度が低下する原 因は、 電解中に陽極において発色剤であるチォ化合物が酸ィヒ^されて効果を失 うためであることを見出し、 チォ化合物を液中で安定ィヒすることによって、 ルテ ニゥムめっき被膜が強レ、黒色度で維持されるとの知見を得た。  The present inventor has found that the cause of the decrease in blackness in such black ruthenium plating is that the thio compound which is a color former is oxidized at the anode during electrolysis and loses its effect. It has been found that by stabilizing the thio compound in the solution, the ruthenium plating film is maintained at a high level and blackness.
この知見に基づき、 本発明は、  Based on this finding, the present invention
1 . 液中の成分として、 硫酸ルテニウム、 スルファミン酸、 チォ化合物及び電解 中の陽極酸化によるチォ化合物の^?を防止するために添加する犠牲酸化剤を含 有することを特徴とする黒色ルテニウムめっき液、  1. Black ruthenium plating solution containing ruthenium sulfate, sulfamic acid, a thio compound and a sacrificial oxidizing agent added to prevent thio compounds from being anodized during electrolysis as components in the solution. ,
2 . 犠牲酸化剤が硫酸ヒドロキシルァミン、 ホルマリン、 ァスコルビン酸から選 択した 1種以上であることを特徴とする上記 1記載の黒色ルテニゥムめっき液、 2. The black ruthenium plating solution as described in 1 above, wherein the sacrificial oxidizing agent is at least one selected from hydroxylamine sulfate, formalin, and ascorbic acid.
3 . チォ化合物がチォ尿素、 チォ尿素誘導体、 メルカプト基を有する化合物、 チ オリンゴ酸、 チォシアン酸アンモンから選択した 1種以上であることを特徴とす る上記 1又は 2記載の黒色ルテニゥムめっき液、 3. The black ruthenium plating solution according to the above 1 or 2, wherein the thio compound is at least one selected from thiourea, a thiourea derivative, a compound having a mercapto group, thiomalic acid, and ammonium thiocyanate.
を提供するものである。 発明の実施の形態 Is provided. Embodiment of the Invention
本発明の黒色ルテニウムめっき液では、 ルテニウムめっき液中に電解中の陽 極酸ィ匕によるチオイヒ合物の^を防止するため犠牲酸化剤を添加する。  In the black ruthenium plating solution of the present invention, a sacrificial oxidizing agent is added to the ruthenium plating solution in order to prevent the formation of a thioic compound due to the positive electrode during electrolysis.
これにより、 陽極では犠牲酸化剤の酸化反応が主反応として進行し、 チォ化 合物の酸化反応はほとんど起こらなくなる。  As a result, the oxidation reaction of the sacrificial oxidant proceeds as the main reaction at the anode, and the oxidation reaction of the thio compound hardly occurs.
そのため、 チォ化合物によるめつき被膜の黒色化する作用及び効果が劣化す ることはなく、 従来は、 上記のように頻繁にチオイヒ合物を添加しなければならな かったのに対して、 チォ化合物の補給を行わなくとも強い黒色度を維持すること が可能となる。  Therefore, the action and effect of the thio compound for blackening the plating film do not deteriorate. Conventionally, the thioic compound had to be added frequently as described above. A strong blackness can be maintained without replenishing the compound.
本発明の黒色ルテニウムめっき液は、 硫酸ノレテニゥム、 スルファミン酸、 チォ 化合物及び電解中の陽極酸化によるチォ化合物の分解を防止するために添加する 犠牲酸化剤を含有する。  The black ruthenium plating solution of the present invention contains norethenium sulfate, sulfamic acid, a thio compound, and a sacrificial oxidizing agent added to prevent decomposition of the thio compound due to anodic oxidation during electrolysis.
硫酸ルテニウムは、 めっき «として析出するルテニウム金属源となり、 ルテ ニゥム濃度としては、 1〜 1 0 g ZLが電流効率、 めっき時間および取扱い中 の電着物の洗浄等によるルテニウムの損失 (いわゆる 「汲み出し」 ) の点から望 ましい。 しかし、 特にこの濃度に限定されるものではない。  Ruthenium sulfate becomes a source of ruthenium metal that precipitates as plating, and the ruthenium concentration is from 1 to 10 g ZL. Current efficiency, plating time and loss of ruthenium due to washing of electrodeposits during handling (so-called “pumping”) ) Is desirable. However, it is not particularly limited to this concentration.
スルファミン酸は、 硫酸ルテニウムを用いた場合における陽極酸化及び陰極還 元によるルテニウムィォン原子価の不安定を抑制し、 金属化しな 1、低原子価ルテ 二ゥムの生成を防止し、 安定したルテニウムめっき作業をすることができるよう にするものである。 この濃度としては 5 0〜1 5 0 g /Lが適当であるが、 特に これらに制限される必要はなレ、。  Sulfamic acid suppresses the instability of ruthenium ion valence due to anodic oxidation and cathodic reduction when ruthenium sulfate is used, prevents the formation of non-metallized, low-valent ruthenium, and provides stable ruthenium. It enables plating work. An appropriate concentration is 50 to 150 g / L, but it is not particularly necessary to limit the concentration.
チオイヒ合物は、 ルテニウムめっき ¾ の色調を黒色化させるために添加するも のであり、 チォ化合物としては、 チォ尿素, チォ尿素誘導体, メルカプト基を有 する化合物、 チォリンゴ酸、 チォシアン酸アンモン等から選択した 1種以上の、 酸性溶液に溶解しうるものが使用できる。 特に、 該化合物の安定性及び価格の点 からチォ尿素が最適である。 チォ化合物の濃度は、 高いほど強い黒色度が得られるが、 逆に高すぎると液が 不安定となる。 濃度としては、 0 . 1〜1 0 . O g /L、 特に 1 . 0〜5 . 0 g / Lが適当である。 The thioic compound is added to blacken the color tone of the ruthenium plating ¾. The thio compound is selected from thiourea, a thiourea derivative, a compound having a mercapto group, thiomalic acid, ammonium thiocyanate, and the like. One or more of those that can be dissolved in an acidic solution can be used. Particularly, thiourea is most suitable in view of the stability and price of the compound. The higher the concentration of the thio compound, the stronger the blackness is obtained, but if the concentration is too high, the solution becomes unstable. A suitable concentration is 0.1 to 10 Og / L, particularly 1.0 to 5.0 g / L.
電解中の陽極酸化によるチォ化合物の分解を防止するために添加する犠牲酸ィ匕 剤としては、 チォ化合物よりも、 陽極酸化を受けやすいものを使用する。  As the sacrificial oxidizing agent added to prevent the decomposition of the thio compound due to anodic oxidation during electrolysis, a sacrificial oxidizing agent that is more susceptible to anodic oxidation than the thio compound is used.
その化合物自身が電解中に陽極酸化を受けて変化し消耗するが、 それ自身や酸 化した化合物がルテニウムの析出反応に影響を及ぼさないことが必要である。 この犠牲酸化剤としては、 硫酸ヒドロキシルァミン、 ホルマリン、 ァスコルビ ン酸等が挙げられる。 特に、 硫酸ヒドロキシルァミンは、 酸ィヒされても液中に残 留してめつき被膜に影響を与えることがないため最も有効である。  The compound itself undergoes anodization during electrolysis and changes and is consumed, but it is necessary that the compound itself and the oxidized compound do not affect the ruthenium deposition reaction. Examples of the sacrificial oxidizing agent include hydroxylamine sulfate, formalin, and ascorbic acid. In particular, hydroxylamine sulphate is the most effective because it remains in the solution even when acidified and does not affect the coating.
この犠牲酸化剤は、 実質的に液中に存在すればチォ化合物の酸化 を防止す る作用があるため、 濃度は特にされるものではないが、 通常 0 . l〜1 0 0 gノ Lが適当である。  The sacrificial oxidizing agent has an effect of preventing oxidation of the thio compound if it is substantially present in the solution. Therefore, the concentration of the sacrificial oxidizing agent is not particularly limited, but usually 0.1 to 100 g L. Appropriate.
本発明の黒色ルテニウムめっき液では、 p H、 電流密度、 液温を適宜調整して 使用することができる。 具体的には、 p Hは 2未満、 電流密度は 5〜1 5 AZ d m 液温は 4 0 °C以上が適当である。  In the black ruthenium plating solution of the present invention, the pH, the current density, and the solution temperature can be appropriately adjusted and used. Specifically, it is appropriate that the pH is less than 2, the current density is 5 to 15 AZdm, and the liquid temperature is 40 ° C or higher.
また、 本発明の黒色ルテニウムめっきを行う基材 (素材) はニッケルめっき上 にフラッシュ金めつきを施したものが適当である。  The substrate (material) on which the black ruthenium plating of the present invention is performed is suitably a nickel plating plated with flash plating.
また、アノードとしては一般的に白金若しくは白金めつきチタンを使用する。 ただし、 これらの条件は、 当該業者が設備や被めつき物の形状等により適宜選 択するべきものであり、 特にこれらに制限される必要はない。 実施例及び比較例  In general, platinum or platinum-plated titanium is used as the anode. However, these conditions should be appropriately selected by the trader according to the equipment and the shape of the covering object, and need not be particularly limited. Examples and comparative examples
以下、 実施例及び比較例に基づいて説明する。 なお、 これらはあくまで一例 であり、 この例に制限されるものではなレ、。 すなわち、 本発明の技術思想に含ま れる他の態様、 変形あるいは例の全てを包含するものである。 下記の,組成のルテニウムめっき液を用意した。 Hereinafter, description will be made based on examples and comparative examples. In addition, these are only examples, and are not limited to these examples. That is, the present invention encompasses all other aspects, modifications, and examples included in the technical concept of the present invention. A ruthenium plating solution having the following composition was prepared.
硫酸ルテニウム (Ruとして) 3 L  Ruthenium sulfate (as Ru) 3 L
スルファミン酸 l O O gZL  Sulfamic acid l O O gZL
チォ尿素 1. 5 g/L  Thiourea 1.5 g / L
次に、 この液を 3部に分け、 2部にそれぞれ犠牲酸化剤として硫酸ヒ ドロキシ ルァミン 10 gZL、 50 gZLをそれぞれ添加して実施例 1及び 2とし、 残り の 1部には添加せず、 これを比較例とした。  Next, this solution was divided into 3 parts, and 2 parts each were added with 10 gZL of hydroxylamine sulfate and 50 gZL as a sacrificial oxidizing agent, respectively, to obtain Examples 1 and 2, and the remaining 1 part was not added. This was used as a comparative example.
この 3種の液を用い、 めっきを繰り返し実施した。 めっき条件は、 次の通りで ある。  Plating was repeatedly performed using these three solutions. The plating conditions are as follows.
(めっき条件)  (Plating conditions)
pH :約 0. 1  pH: about 0.1
: 5 A/dm2 : 5 A / dm 2
液温 : 50。C  Liquid temperature: 50. C
: 白金板  : Platinum plate
めっき時間 : 30分 Z回  Plating time: 30 minutes Z times
素材は、 通常のワット浴で N iめっきした真鍮板に、 フラッシュ金めつきし たものを使用した。  The material used was a brass plate plated with Ni in a normal watt bath and flash-flashed.
通電量 5 Ahノ L毎に得られためっき被膜の状態等観察し、 その結果を表 1に 示す。  The state of the plating film obtained for every 5 Ah of current was observed, and the results are shown in Table 1.
なお、 実施例 1では犠牲酸化剤である硫酸ヒ ドロキシルァミンを多量に添加 しているため、 黒色のルテニウムめっきの途中で、 同剤を補給する必要がなかつ たが、 実施例 2では電解中に犠牲酸ィ匕剤である硫酸ヒドロキシルァミンがめっき 初期の添加量が少なく、 またこれがめっきとともに消耗するので、 濃度を維持す るために補給を行った。  In Example 1, since a large amount of sacrificial oxidizing agent, hydroxylamine was added, it was not necessary to supply the same agent during black ruthenium plating, but in Example 2, sacrificed during electrolysis. Since the amount of hydroxylamine sulfate, which is an acidifying agent, was small in the initial stage of plating and was consumed with plating, replenishment was performed to maintain the concentration.
実施例 1及び 2では、 安定的に黒色のルテニウムめっき被膜が継続的に安定し て得られた。 これに対し、 比較例では度々チォ尿素を補給しなければ、 黒色の被膜が得られ ず、 その黒色度も、 めっき初期においては弱い黒色の被膜であり、 めっきの進行 とともにやや黒っぽい銀色の被膜となり、 さらに 2 5 A h / L及び 3 0 A h / L の段階でチォ尿素を 3 g / Lをそれぞれ添加すると、 光沢のない灰茶色の被膜が 形成され、 めっき液に濁りを生じていた。 In Examples 1 and 2, black ruthenium plating films were obtained stably and continuously. On the other hand, in the comparative example, if thiourea was not replenished frequently, a black film could not be obtained, and the blackness was a weak black film at the beginning of plating, and became a slightly blackish silver film as plating progressed. When thiourea was added at 3 g / L at the stages of 25 Ah / L and 30 Ah / L, respectively, a dull gray-brown film was formed, and the plating solution was turbid.
このように、 チォ尿素を補給し過ぎると、 液に濁りが生じて不安定となり、 強 い黒色被膜は形成されず、 良好なめっき «は得られなくなった。  Thus, when thiourea was replenished too much, the solution became turbid and became unstable, a strong black film was not formed, and good plating could not be obtained.
このように、 本発明の犠牲酸化剤として硫酸ヒドロキシルァミンを添加するこ とにより、 黒色ルテニウムめっきでは強い黒色度のめっき被膜を安定的に得るこ とが可能となった。 また、 硫酸ヒドロキシノレアミン等の犠牲酸化剤は、 黒色ルテ ニゥムめっき被膜の形成に一切の障害となることはなかつた。  Thus, by adding hydroxylamine sulfate as the sacrificial oxidizing agent of the present invention, it became possible to stably obtain a plating film having a strong blackness in black ruthenium plating. In addition, a sacrificial oxidizing agent such as hydroxynoramine sulfate did not hinder the formation of a black ruthenium plating film.
犠牲酸化剤として硫酸ヒ ドロキシルァミンは最も効果的であつたが、 本発明 の他の犠牲酸化剤もほぼ同様な効果が得られた。 また、 チォ尿素以外のチォ化合 物でも同様の結果が得られた。  Hydroxylamine sulfate was the most effective as a sacrificial oxidizing agent, but other sacrificial oxidizing agents of the present invention obtained almost the same effect. Similar results were obtained with thio compounds other than thiourea.
5Ah/L 謹/し 15Ah/L 20Ah/し 25AVL 30Ah/L 実施例 黒色被膜 黒色被膜 黒色被膜 黒色被膜 黒色被膜 黒色被膜5Ah / L Gentle / Less 15Ah / L 20Ah / L 25AVL 30Ah / L Example Black coating Black coating Black coating Black coating Black coating Black coating
1 1
黒色謹 黒色被膜 黒色被膜 黒色被膜 黒色被膜 実施例 黒色被膜 硫酸ヒドロ 硫酸ヒにロ 硫酸ヒ ロ 硫酸ヒにロ 硫酸ヒドロキ Black coating Black coating Black coating Black coating Black coating Example Black coating Sulfuric acid sulfate Sulfuric acid sulfate Sulfuric acid sulfate sulfuric acid Hydroxy sulfate
2 キシルァミン キシルァミン キシルァミン キシルァミン シルァミン 5g 2 xylamine xylamine xylamine xylamine xylamine 5g
5g/L補給 5g/L補給 5g/L補給 5g/L補給 /L補給 チォ尿素 1. チォ尿素 1. チォ尿素 1. チォ尿素 3g チォ尿素 3g/ 5 g / L supply 5 g / L supply 5 g / L supply 5 g / L supply / L supply Thiourea 1. Thiourea 1. Thiourea 1. Thiourea 3 g Thiourea 3 g /
5g/Lを添 5g/Lを添 5g几を添 /Lを添加 Lを添加 比較例 弱い黒色 加 加 加 光沢のな 光沢のな の被膜 やや黒つ やや黒つ やや つ い灰茶色 い灰茶色 ぼい銀色 ぼい銀色 ぼい銀色 の被膜 の被膜 の被膜 の被膜 の被膜 液に濁り 液に濁り 発明の効果 Add 5g / L Add 5g / L Add 5g geometry / Add L Add L Comparative example Weak black Addition Glossy glossy film Slightly blackish Slightly blackish Slightly brownish grayish brown Blur silver Blur silver Blur silver coat Turbine liquid Turbid liquid The invention's effect
黒色ルテニウムめっきにおける黒色度が低下する原因は、 電解中に陽極にお いて発色剤であるチォ化合物が酸化分解されて効果を失うためであり、 チォ化合 物を液中で安定化することによって、 ルテニウムめっき被膜が強い黒色度で維持 することができる。 そのため、 黒色ルテニウムめっき液中に電解中の陽極酸化に よるチォ化合物の分解を防止するための犠牲酸化剤を添加する。 これにより、 陽 極では犠牲酸化剤の酸化反応が主反応として進行し、 チォ化合物の酸化反応はほ とんど起こらなくなるという著しい効果があった。  The reason why the blackness of black ruthenium plating decreases is that the thio compound, which is a color former, is oxidatively decomposed at the anode during electrolysis and loses its effect.By stabilizing the thio compound in the solution, The ruthenium plating film can maintain a strong blackness. Therefore, a sacrificial oxidizing agent is added to the black ruthenium plating solution to prevent decomposition of the thio compound due to anodic oxidation during electrolysis. As a result, at the anode, the oxidation reaction of the sacrificial oxidant proceeds as a main reaction, and the oxidation reaction of the thio compound hardly occurs.
そして従来の黒色ルテニウムめっき液の特性、 すなわち液の管理が容易であ り、 しかも光沢を有し基材との密着性がよく、 耐食性及び耐摩耗性に優れている という黒色ルテニゥムめっき液本来の特徴を生かすと共に、 上記犠牲酸ィヒ剤は発 色剤として添加するチオイ匕合物が電解中の陽極酸ィ匕によって するのを抑制し、 電解の工程中において強い黒色度を維持して、 安定した黒色めつきを得ることが できるという優れた効果を有する。  The characteristics of the conventional black ruthenium plating solution, that is, the easy management of the solution, the glossiness, good adhesion to the substrate, and excellent corrosion resistance and abrasion resistance are the original characteristics of the black ruthenium plating solution. In addition to utilizing the features, the sacrificial acid suppresses the thiol conjugate added as a coloring agent by anodic oxidation during electrolysis, and maintains a strong blackness during the electrolysis process. It has an excellent effect that a stable black plating can be obtained.

Claims

請 求 の 範 囲 The scope of the claims
1 . 液中の成分として、 硫酸ルテニウム、 スルファミン酸、 チォ化合物及び電解 中の陽極酸化によるチオイヒ合物の を防止するために添加する犠牲酸化剤を含 有することを特徴とする黒色ルテニウムめっき液。 1. A black ruthenium plating solution comprising, as components in the solution, ruthenium sulfate, sulfamic acid, a thio compound, and a sacrificial oxidizing agent added to prevent thioic acid compounds due to anodic oxidation during electrolysis.
2 . 犠牲酸化剤が硫酸ヒ ドロキシノレアミン、 ホルマリン、 ァスコルビン酸から選 択した 1種以上であることを特徴とする請求の範囲 1記載の黒色ルテニゥムめつ き液。  2. The black ruthenium plating solution according to claim 1, wherein the sacrificial oxidizing agent is at least one selected from hydroxyxoleamine sulfate, formalin, and ascorbic acid.
3 . チォ化合物がチォ尿素、 チォ尿素誘導体、 メルカプト基を有する化合物、 チ オリンゴ酸、 チォシアン酸アンモンから選択した 1種以上であることを特徴とす る請求の範囲 1又は 2記載の黒色ルテニゥムめっき液。  3. The black ruthenium plating according to claim 1 or 2, wherein the thio compound is at least one selected from thiourea, a thiourea derivative, a compound having a mercapto group, thiomalic acid, and ammonium thiocyanate. liquid.
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